JP3100349B2 - Method for producing polyurethane foam - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a polyurethane foam. More specifically, the present invention relates to a method for producing a polyurethane foam having high mechanical strength and suitably used as shoe soles and the like, and a polyester polyol used as a raw material of the polyurethane foam.

[0002]

2. Description of the Related Art Polyurethane foam is a resin foam excellent in impact resistance, chemical resistance, abrasion resistance, cold resistance and the like. By appropriately combining a polyol and a polyisocyanate, which are raw materials for such a polyurethane foam, a polyurethane foam having a wide range of properties from hard to soft can be produced.

When a rigid polyurethane foam is produced, a polyfunctional polyol having a relatively low molecular weight is used as the polyol. When a flexible polyurethane foam is produced, a polyol having a relatively high molecular weight and a low functional group number such as a polyester polyol or a polyether polyol is used. The polyurethane foam is manufactured by mixing a foaming agent such as water and chlorofluorocarbon into a polyol, and by adjusting the amount of the foaming agent, the density of the obtained polyurethane foam can be set to a predetermined value. .

In general, when producing a molded article of a polyurethane foam, it is preferable that the density of the polyurethane foam is low, because the cost is low. However, when the density is lowered, the amount of resin per unit volume is reduced. Strength decreases.

Therefore, it has been proposed to add a crosslinking agent, a polyfunctional polyol, an aromatic polyol or the like to the polyol in order to improve the mechanical strength of the molded article.

However, when a cross-linking agent or a polyfunctional polyol is used in preparing an isocyanate prepolymer, there is a problem that gelation is caused. When an aromatic polyol is used, the viscosity and melting point of the aromatic polyol are extremely high. Therefore, when producing a polyurethane foam from a prepolymer obtained using the aromatic polyol, the polyurethane polyol is used. There is a problem that it is difficult to adjust the viscosity and the melting point of the prepolymer suitable for the production conditions of the foam.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above prior art, and has a low density, a good appearance and a good feeling, and a mechanical strength such as a tensile strength and a tear strength. An object of the present invention is to provide a method for producing an excellent polyurethane foam.

[0008]

Gist of the present invention SUMMARY OF THE INVENTION from (1) (a) and terephthalic acid and (b) adipic acid
Becomes, (a) terephthalic acid / (b) an acid component molar ratio of adipic acid is 0.05 to 0.3, polyvalent polyester polyol and alcohol obtained by condensation polymerization, (2) number average molecular weight 500 (3) the polyester polyol according to the above (1), wherein the polyhydric alcohol has ethylene glycol and / or
Or (4) the polyester polyol according to (1) or (2), which is 1,4-butanediol; (4) a method of producing a polyurethane foam by reacting and foaming a polyisocyanate component and a polyol component, wherein the polyol component is (a) consists of a terephthalic acid and (b) adipic acid, (a) terephthalic acid /
(B) A method for producing a polyurethane foam, comprising a polyester polyol obtained by condensation polymerization of an acid component having a molar ratio of adipic acid of 0.05 to 0.3 and a polyhydric alcohol. (5) The above (4), wherein the content of the polyester polyol in the polyol component is 10 to 80% by weight.
(6) A method for producing a polyurethane foam by reacting and foaming an isocyanate prepolymer prepared from a polyisocyanate component and a polyol component with a polyol component, wherein the isocyanate prepolymer is used for the isocyanate prepolymer. polyol component for the consist (a) and terephthalic acid and (b) adipic acid, (a) terephthalic acid /
(B) A method for producing a polyurethane foam, comprising a polyester polyol obtained by condensation polymerization of an acid component having a molar ratio of adipic acid of 0.05 to 0.3 and a polyhydric alcohol. About.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester polyol of the present invention is useful as a raw material for producing a polyurethane foam, as described later.

As described above, the polyester polyol of the present invention comprises (a) terephthalic acid and (b) adipic acid.
From it, it is obtained by polycondensation an acid component and a polyhydric alcohol is 0.05 to 0.3 molar ratio of (a) terephthalic acid / (b) adipic acid.

The molar ratio of (a) terephthalic acid / (b) adipic acid is 0.05 or more so as not to increase the freezing point and to give a liquid under molding conditions (molding temperature: about 40 ° C.). , Preferably 0.08 or more, and 0.3 or less, especially 0.25 or less, more preferably 0.15 or less, in order to prevent the viscosity from being too high to make injection or injection difficult during molding. It is. When the obtained polyester polyol is used as a polyol component when producing a polyurethane foam, the molar ratio of (a) terephthalic acid / (b) adipic acid is as follows:
0.25 or less, preferably 0.15 or less, further 0.1
It is desirably 2 or less.

As the polyhydric alcohol, ethylene glycol and / or 1,4-butanediol can be suitably used in the present invention.

The polyester polyol of the present invention is obtained by polycondensing the above-mentioned acid component with a polyhydric alcohol in an amount in which the polyhydric alcohol becomes excessive.

The number average molecular weight of the polyester polyol of the present invention is from 500 to 300 from the viewpoint of viscosity and melting point.
0, preferably 1000 to 2500.

The method for producing a polyurethane foam of the present invention has a great feature in that the polyester polyol is used. Thus, in the present invention,
By using the polyester polyol, the obtained polyurethane foam has excellent mechanical strength.

The method for producing the polyurethane foam of the present invention using the polyester polyol mainly includes:
There are the following two methods.

That is, (1) when a polyisocyanate component and a polyol component are reacted and foamed to produce a polyurethane foam,
As the polyol component consists of a (a) terephthalic acid and (b) adipic acid, (a) terephthalic acid /
(B) a method using a polyester component obtained by condensation polymerization of an acid component having a molar ratio of adipic acid of 0.05 to 0.3 and a polyhydric alcohol (hereinafter, referred to as production method I), and (2) When the isocyanate prepolymer prepared from the polyisocyanate component and the polyol component is reacted with the polyol component and foamed to produce a polyurethane foam, the polyol component used in the isocyanate prepolymer is (a) Terephthalic acid and (b)
Consists adipic acid, an acid component is 0.05 to 0.3 molar ratio of (a) terephthalic acid / (b) adipic acid,
There is a method using a polyester polyol containing a polycondensation with a polyhydric alcohol (hereinafter referred to as production method II).

First, the manufacturing method I will be described.

In the production method I, as the polyol component used when the polyisocyanate component and the polyol component are reacted and foamed, those containing the polyester polyol described in detail above can be used.

As the polyol component, a polyol other than the polyester polyol is used. Such polyols include, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,4-
Butanediol, 1,5-pentanediol, methylpentanediol, 1,6-hexanediol, trimethylolpropane, glycerin, pentaerythritol,
Obtained by polycondensing at least one polyhydric alcohol such as diglycerin, dextrose and sorbitol with at least one dibasic acid such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid and dimer acid. Polyether polyols such as polyester polyol, polypropylene glycol, polyoxytetramethylene glycol, etc., polycaprolactone polyol, polycarbonate polyol, and the like, and these can be used alone or in combination of two or more.

The content of the polyester polyol in the polyol component is preferably from 10 to 80% by weight, from the viewpoint of suitably maintaining the liquidity and viscosity of the polyol component and producing a polyurethane foam having excellent mechanical strength. Is 20 to 70% by weight, more preferably 4% by weight.
Desirably, it is 0 to 60% by weight.

In the present invention, if necessary, for example, a chain extender, a foaming agent, a urethanizing catalyst, a foam stabilizer, a stabilizer, a pigment, etc. may be added to the polyol component in appropriate amounts. Good.

As the chain extender, a compound having a low molecular weight and having two or more active hydrogens in a molecule can be used. Representative examples of such chain extenders include, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, methylpentanediol, 1,6-hexanediol, trimethylolpropane, glycerin , Polyhydric alcohols such as pentaerythritol, diglycerin, dextrose, sorbitol, ethylenediamine,
Examples thereof include aliphatic polyamines such as hexamethylenediamine, aromatic polyamines, and alkanolamines such as diethanolamine, triethanolamine, and diisopropanolamine.

Examples of the blowing agent include water and fluorocarbons such as trichlorofluoromethane, dichlorodifluoromethane, and trichlorodifluoroethane. These blowing agents may be used alone or in combination of two or more. Can be used.

Examples of the urethanization catalyst include triethylamine, triethylenediamine, N-methylmorpholine, N-ethylmorpholine, N, N, N ', N'.
Tertiary amines such as tetramethylhexamethylenediamine, 1,2-dimethylimidazole, N, N'-diethylbenzylamine, tin (II) acetate, tin octoate (I
I), tin (II) laurate, dibutyltin dilaurate,
And tin compounds such as dibutyltin dimaleate, dioctyltin diacetate, and dibutyltin dichloride.
These urethanization catalysts can be used alone or in combination of two or more.

Examples of the foam stabilizer include silicone surfactants such as dimethylpolysiloxane, polyoxyalkylene polyol-modified dimethylpolysiloxane, and alkylene glycol-modified dimethylpolysiloxane, fatty acid salts, sulfate salts, phosphate salts, and the like. And anionic surfactants such as sulfonates.

Examples of the stabilizer include dibutylhydroxytoluene, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], isooctyl-3- (3,5
Hindered phenolic radical scavengers such as -di-t-butyl-4-hydroxyphenyl) propionate;
Antioxidants such as phosphites such as phosphorous acid, triphenylphosphite, triethylphosphite, and triphenylphosphine; 2- (5-methyl-2-hydroxyphenyl) benzotriazole, methyl-3- [3
-T-butyl-5- (2H-benzotriazole-2-
Yl) -4-hydroxyphenyl] propionate and polyethylene glycol.

Examples of the pigment include an inorganic pigment represented by a transition metal salt, an organic pigment represented by an azo compound, and carbon powder. However, the present invention is not limited to these examples. .

The polyol component thus obtained is in a liquid state at room temperature and can be injected even at a low pressure. Therefore, by reacting with a polyisocyanate component described later, a polyurethane foam can be molded without any problem.

Next, regarding the polyisocyanate component used in the above-mentioned production method I, typical examples of the polyisocyanate component include isocyanate prepolymers.

The isocyanate prepolymer is obtained by stirring and reacting a polyisocyanate monomer and a polyol, if necessary, with an additive such as a stabilizer by a conventional method in the presence of an excess of the polyisocyanate monomer.

Specific examples of the polyisocyanate monomer include, for example, tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymethylene Polyphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3 '
Polyisocyanate compounds such as -dimethyl-4,4'-diphenylmethane diisocyanate, 3,3-dichloro-4,4'-biphenylene diisocyanate, and 1,5-naphthalenediisocyanate, and modified products thereof, for example, carbodiimide modified products. . These polyisocyanate monomers can be used alone or in combination of two or more. Of these, 4,
The use of 4'-diphenylmethane diisocyanate alone or in combination with the 4,4'-diphenylmethane diisocyanate and its modified carbodiimide is particularly preferred in the present invention.

Examples of the polyol include ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, methylpentanediol, 1,6-hexanediol, trimethylolpropane, glycerin and pentane. Polycondensation of at least one polyhydric alcohol such as erythritol, diglycerin, dextrose and sorbitol with at least one dibasic acid such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid and dimer acid Polyether polyols such as polyester polyol, polypropylene glycol, polyoxytetramethylene glycol obtained by the above, polycaprolactone polyol, polycarbonate polyol and the like, and these are used alone. Others can be used in combination of two or more.

In preparing the isocyanate prepolymer, various additives may be added, if necessary.

The additives include, for example, additives used as needed in preparing the polyester polyol, and hydrogen chloride gas, sulfur dioxide gas, and the like in order to prevent the isocyanate prepolymer from self-polymerizing. Acid gases such as acetyl chloride, benzoyl chloride,
An isocyanate self-polymerization inhibitor such as an acid chloride such as isophthalic acid chloride and a phosphoric acid compound such as phosphoric acid, monoethyl phosphate and diethyl phosphate can be used. These additives can be used alone or in combination of two or more.

NCO of the above isocyanate prepolymer
% Is not less than 15%, preferably 17%, so as not to increase the viscosity and make molding with a low-pressure foaming machine difficult.
% Or more, and in order to avoid a decrease in viscosity and a decrease in the measuring accuracy of the foaming machine, 25%
Or less, preferably 22% or less.

The isocyanate prepolymer comprises 15
Since it exhibits a liquid state at a temperature of at least ℃ and can be discharged even at a low pressure, it can be used for producing a polyurethane foam without any problem even at a molding temperature of, for example, 40 to 50 ℃.

In the production method I, when reacting the polyol component with the polyisocyanate component, it is preferable to adjust the ratio between the two so that the isocyanate index becomes 95 to 105.

In the production method I, a polyol component and a polyisocyanate component are mixed and stirred by a molding machine.
By injecting into a molding die and foaming, a polyurethane foam can be molded. More specifically, for example, after adjusting the temperature of the polyol component to about 40 ° C. using a tank or the like, and then using a foaming machine such as an automatic mixing injection type foaming machine or an automatic mixing injection foaming machine, the polyisocyanate is used. By reacting with the components, a polyurethane foam can be formed.

According to the production method I, after the polyol component and the polyisocyanate component are mixed, the mixture is usually mixed with 40 to 40%.
It can be formed into urethane shoe soles by a foaming machine adjusted to about 50 ° C.

Incidentally, the production method I can be employed for the production of a non-foamed elastomer. However, when it is used for the production of shoe soles, the resulting polyurethane foam has a reduced resin content per unit volume. Nevertheless, mechanical strength such as tensile strength and tear strength can be sufficiently improved.

Next, the production method II will be described.

In the production method II, when an isocyanate prepolymer comprising a polyisocyanate component and a polyol component is reacted with a polyol component to produce a polyurethane foam, the polyol component used in the isocyanate prepolymer is: (A) Terephthalic acid and (b) adipic acid, wherein terephthalic acid /
What contains a polyester polyol obtained by polycondensing an acid component having a molar ratio of adipic acid of 0.05 to 0.3 and a polyhydric alcohol is used.

The polyisocyanate component which is a raw material for producing the isocyanate prepolymer includes, for example, the polyisocyanate monomer used in the above-mentioned production method I.

As specific examples of the polyisocyanate monomer, the same as the specific examples of the polyisocyanate monomer used in the above-mentioned production method I are exemplified. In these examples, the use of 4,4'-diphenylmethane diisocyanate alone or the combined use of 4,4'-diphenylmethane diisocyanate and its modified carbodiimide is particularly preferred in the present invention.

As the polyol component as a raw material for producing the isocyanate prepolymer, those containing the polyester polyol described in detail above are used.

In the production method II, since the viscosity of the obtained isocyanate prepolymer can be suitably maintained by using the above-mentioned polyester polyol, it is necessary to give a polyurethane foam having excellent mechanical strength. Can be.

As the polyol component, a polyol other than the above-mentioned polyester polyol is used. As the polyol, for example, the same polyols as those used in Production Method I are exemplified.

The content of the polyester polyol in the polyol component is desirably 23 to 58% by weight, preferably 31 to 52% by weight.

The ratio between the polyisocyanate component and the polyol component is such that the equivalent ratio of NCO groups / OH groups is usually
It is desirable to adjust so as to be about 5 to 30.

When preparing the isocyanate prepolymer, additives such as a self-polymerization inhibitor, an antioxidant and an ultraviolet absorber may be added as required.

As the self-polymerization inhibitor, the production method I
And the same self-polymerization inhibitors that can be added when preparing the isocyanate prepolymer.

Examples of the antioxidant and the ultraviolet absorber include those which can be added to the polypolyol component used in the above-mentioned production method I.

Next, an isocyanate prepolymer is obtained by stirring and reacting the polyisocyanate component, the polyol component and, if necessary, additives in a conventional manner.

The NCO% of the thus obtained isocyanate prepolymer is desirably 12% or more, preferably 14% or more, in order to prevent the viscosity from increasing and molding with a low-pressure foaming machine becomes difficult. Further, in order to prevent the viscosity from being lowered and the measuring accuracy of the foaming machine from being lowered, it is desirable that it is 25% or less, preferably 22% or less.

The isocyanate prepolymer is 15
Since it exhibits a liquid state at a temperature of at least ℃ and can be discharged even at a low pressure, it can be used for producing a polyurethane foam without any problem even at a molding temperature of, for example, 40 to 50 ℃.

Next, a polyurethane foam is obtained by reacting and foaming the isocyanate prepolymer and the polyol component.

Examples of the polyol component used for the reaction with the isocyanate prepolymer include the same polyols other than the polyester polyol used for the polyol component in Production Method I.

The polyol component used for the reaction with the isocyanate prepolymer may include, if necessary,
A chain extender, a foaming agent, a urethanization catalyst, a stabilizer, a pigment, and the like may be appropriately added in appropriate amounts. Examples of these components are the same as those that can be added to the polyol component used in the production method I.

In the production method II, when reacting the polyol component and the polyisocyanate component, it is preferable to adjust the ratio between the two so that the isocyanate index becomes 95 to 105.

In the production method II, a polyurethane foam can be molded by mixing, stirring, injecting into a molding die, and foaming an isocyanate prepolymer, a polyol component and, if necessary, an additive. More specifically, for example, after adjusting the temperature of the polyol component to about 40 ° C. using a tank or the like,
A polyurethane foam can be molded by reacting with an isocyanate prepolymer using a foaming machine such as an automatic mixing injection type foaming machine and an automatic mixing injection type foaming machine.

Further, according to the production method II, after mixing the isocyanate prepolymer and the polyol component, the mixture can be molded into urethane shoe soles by a foaming machine usually adjusted to about 40 to 50 ° C.

The production method II can be used for the production of a non-foamed elastomer. However, when the production method II is used for the production of shoe soles, the resulting polyurethane foam has a reduced resin content per unit volume. Nevertheless, mechanical strength such as tensile strength and tear strength can be sufficiently improved.

Thus, the density of the polyurethane foam obtained by the above-mentioned production method I or production method II is such that a sufficient mechanical strength can be obtained and the density can be reduced.
0.15 to 1.0 g / cm ³ , preferably 0.2 to 0.1 g / cm ³ .
The case of 6 g / cm ³ is practical.

[0065]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following, “parts” means “parts by weight”.

Preparation Example 1 (Production of Polyester Polyol) In a four-necked flask, 100 parts of adipic acid, 12.6 parts of terephthalic acid and 51.1 parts of ethylene glycol were charged, and then a stirring rod, a dehydrating tube, and nitrogen gas were added. An inlet tube and thermometer were attached to the flask. The molar ratio of terephthalic acid / adipic acid was 0.11.

Next, nitrogen gas was introduced into the flask,
The generated water was distilled off while paying attention to bumping, and the temperature was raised to 220 ° C.

After confirming that the inside of the tank became transparent, the pressure was gradually reduced, and water was further distilled off.

The polyester polyol A was obtained by continuing the reaction until the acid value of the obtained reaction solution became 1 KOH mg / g or less.

As physical properties of the obtained polyester polyol A, an acid value, a hydroxyl value, a viscosity, a freezing point and a number average molecular weight were examined.

The acid value is JIS K 0070 and the hydroxyl value is J
IS K 0070, viscosity is JIS Z 8803, freezing point is JIS K 006
Measured according to 5. The number average molecular weight was calculated from the hydroxyl value.

As a result, the obtained polyester polyol A had an acid value of 0.86 KOHmg / g and a hydroxyl value of 51.4 KO.
Hmg / g, viscosity at 60 ° C was 1900 cP, freezing point was 22 ° C, and number average molecular weight was 2147.

Preparation Example 2 (Production of Polyester Polyol) In a four-necked flask, 100 parts of adipic acid, 12.6 parts of terephthalic acid and 75.2 parts of 1,4-butanediol were charged. A tube, a nitrogen gas inlet tube and a thermometer were attached. The value of the molar ratio of terephthalic acid / adipic acid was 0.11.

Next, nitrogen gas was introduced into the flask,
The generated water was distilled off while paying attention to bumping, and the temperature was raised to 220 ° C.

After confirming that the inside of the tank became transparent, the pressure was gradually reduced, and water was further distilled off.

The polyester polyol B was obtained by continuing the reaction until the acid value of the obtained reaction solution became 1 KOH mg / g or less.

As the physical properties of the obtained polyester polyol B, an acid value, a hydroxyl value, a viscosity, a freezing point and a number average molecular weight were examined in the same manner as in Production Example 1.

As a result, the obtained polyester polyol B had an acid value of 0.93 KOH mg / g and a hydroxyl value of 50.4 KO.
Hmg / g, viscosity at 60 ° C was 2250 cP, freezing point was 27 ° C, and number average molecular weight was 2186.

Production Example 1 (Production of Polyol Solution) 40 parts of the polyester polyol A obtained in Preparation Example 1,
60 parts of polyester polyol (ethylene diethylene adipate, number average molecular weight 1,300), 11 parts of ethylene glycol as a chain extender, and 1.05 of water as a foaming agent
Parts, 0.8 part of triethylenediamine as a catalyst and 1 part of a silicone foam stabilizer were mixed, the temperature was adjusted to 60 ° C., and the mixture was stirred to obtain a polyol solution 1.

The physical properties of the obtained polyol solution 1 are as follows:
The acid value, hydroxyl value and viscosity were examined in the same manner as in Preparation Example 1, and the water content was examined according to JIS K0068.

As a result, the resulting polyol solution 1 had an acid value of 0.21 KOHmg / g and a hydroxyl value of 237.5 KOHmg / g.
g, water content is 0.91% by weight, viscosity at 40 ° C. is 1
It was 480 cP.

Production Example 2 (Production of Polyol Solution) Polyester polyol A (40) obtained in Preparation Example 1
Parts), polyester polyol (ethylene-1,4-butanediol adipate, number average molecular weight 1,300) 6
0 parts, 11 parts of ethylene glycol as a chain extender, 1.05 parts of water as a foaming agent, 0.8 parts of triethylenediamine as a catalyst and 1 part of a silicone-based foam stabilizer were mixed.
The temperature was adjusted to 0 ° C., and the mixture was stirred to obtain a polyol solution 2.

When the physical properties of the obtained polyol solution 2 were examined in the same manner as in Production Example 1, the acid value was 0.35 KOHmg /
g, hydroxyl value: 238.4 KOHmg / g, water content: 0.92
The viscosity at 40 ° C. by weight was 1520 cP.

Production Example 3 (Production of Polyol Solution) The polyester polyol A (60
Parts), polyester polyol (ethylene-1,4-butanediol adipate, number average molecular weight 1,300) 4
0 parts, 11 parts of ethylene glycol as a chain extender, 1.05 parts of water as a foaming agent, 0.8 parts of triethylenediamine as a catalyst and 1 part of a silicone-based foam stabilizer were mixed.
The temperature was adjusted to 0 ° C., and the mixture was stirred to obtain a polyol solution 3.

The acid value of the obtained polyol solution 3 was 0.2
1 KOHmg / g, hydroxyl value: 232.1 KOHmg / g, water content: 0.91% by weight, viscosity at 40 ° C .: 18870 cP
I met.

Production Example 4 (Production of Polyol Solution) Polyester polyol B (40) obtained in Preparation Example 2
Parts), polyester polyol (ethylene-1,4-butanediol adipate, number average molecular weight 1,300) 6
0 parts, 11 parts of ethylene glycol as a chain extender, 1.05 parts of water as a foaming agent, 0.8 parts of triethylenediamine as a catalyst and 1 part of a silicone-based foam stabilizer, 6
The temperature was adjusted to 0 ° C., and the mixture was stirred to obtain a polyol solution 4.

The acid value of the obtained polyol solution 4 was 0.1
8 KOH mg / g, hydroxyl value was 238.3 KOH mg / g, water content was 0.91% by weight, and viscosity at 40 ° C. was 1560 cP.

Production Example 5 (Production of Polyol Solution) 40 parts of a polyester polyol (ethylene-1,4-butanediol adipate, number average molecular weight 2,200),
60 parts of polyester polyol (ethylene-1,4-butanediol adipate, number average molecular weight 1,300),
11 parts of ethylene glycol as a chain extender, 1.05 parts of water as a foaming agent, and 0.1 part of triethylenediamine as a catalyst.
8 parts and 1 part of a silicone foam stabilizer were charged, the temperature was adjusted to 60 ° C., and the mixture was stirred to obtain a polyol solution 5.

The acid value of the obtained polyol solution 5 was 0.2
1 KOH mg / g, hydroxyl value was 232.0 KOH mg / g, water content was 0.91% by weight, and viscosity at 40 ° C. was 1210 cP.

Examples 1 to 4 The polyol solutions 1 to 4 obtained in Production Examples 1 to 4 and an isocyanate prepolymer (trade name: B-
2009, NCO%: 18.5%) and an automatic mixing type injection foaming machine (Polyurethane Engineering Co., Ltd., Model MU)
-203S, Model No. 6-018) and foamed under the following molding conditions to produce a polyurethane foam sheet of 10 mm x 100 mm x 30 mm. Table 1 shows the polyol solutions used in each example.

[Molding conditions] Isocyanate index: 100 to 103 Mixing temperature: The temperature of each of the isocyanate prepolymer and the polyol component was adjusted to 35 to 45 ° C. Reactivity: Cream time 5-10 seconds Silk time 15-25 seconds Rise time 35-60 seconds Tack free time 30-55 seconds Demold time 4.5-5.5 minutes Mold: mold temperature 45-55 ° C Release agent silicone and wax density: free foam density 0.12~0.32g / cm ³ green density 0.35 g / cm ³ ripening conditions: 1 week at room temperature

Next, as physical properties of the obtained sheet, C
Hardness, tensile strength (tensile strength), tear strength, elongation at break) were measured according to the following methods. Table 1 shows the results.

[Physical Properties of Sheet] C hardness (ASKER-C): Measured according to SRIS 0101 Tensile strength: JIS K using JIS No. 1 dumbbell
Measured in accordance with 6301 Tear strength: Measured in accordance with JIS K 7311 Breaking elongation: Measured in accordance with JIS K 6301 using JIS No. 1 dumbbell

Comparative Example 1 In Example 1, the polyol solution 5 obtained in Production Example 5 and the isocyanate prepolymer (Kao Corporation) were used as the polyol solution and the isocyanate prepolymer.
Polyurethane foam sheet was produced in the same manner as in Example 1 except that B-2009; NCO%: 18.5%) was used.

The physical properties of the obtained polyurethane foam sheet were examined in the same manner as in Example 1. Table 1 shows the results.

[0096]

[Table 1]

From the results shown in Table 1, the polyurethane foam sheets obtained in Examples 1 to 4 had the same tensile strength and tear strength as Comparative Example 1 while having the same density of the compact. It turns out that it is remarkably excellent.

Preparation Example 3 (Production of Polyester Polyol) In a four-necked flask, 100 parts of adipic acid, 2.27 parts of terephthalic acid and 46.9 parts of ethylene glycol were charged, and then a stirring rod, a dehydrating tube, and nitrogen gas were added. The inlet tube and thermometer were fitted. In addition, the value of the molar ratio of terephthalic acid / adipic acid was 0.02.

Next, nitrogen gas was introduced into the flask,
The generated water was distilled off while paying attention to bumping, and the temperature was raised to 220 ° C.

After confirming that the inside of the tank became transparent, the pressure was gradually reduced, and water was further distilled off.

The reaction was continued until the acid value of the obtained reaction solution became 1 KOH mg / g or less, whereby a white solid polyester polyol C was obtained.

As the physical properties of the obtained polyester polyol C, an acid value, a hydroxyl value, a viscosity, a freezing point and a number average molecular weight were examined in the same manner as in Production Example 1.

As a result, the obtained polyester polyol C had an acid value of 0.35 KOHmg / g and a hydroxyl value of 50.4 KO.
Hmg / g, viscosity at 60 ° C was 1400 cP, freezing point was 48 ° C, and number average molecular weight was 2211.

Preparation Example 4 (Production of Polyester Polyol) In a four-necked flask, 100 parts of adipic acid, 45.8 parts of terephthalic acid, and 64.6 parts of ethylene glycol were charged, and then a stirring rod, a dehydrating tube, and nitrogen gas were added. The inlet tube and thermometer were fitted. The molar ratio of terephthalic acid / adipic acid was 0.40.

Next, nitrogen gas was introduced into the flask,
The generated water was distilled off while paying attention to bumping, and the temperature was raised to 220 ° C.

After confirming that the inside of the tank became transparent, the pressure was gradually reduced, and water was further distilled off.

The reaction was continued until the acid value of the obtained reaction solution became 1 KOH mg / g or less, whereby a transparent solid polyester polyol D was obtained.

As physical properties of the obtained polyester polyol D, an acid value, a hydroxyl value, a viscosity, a freezing point and a number average molecular weight were examined in the same manner as in Production Example 1.

The resulting polyester polyol D had an acid value of 0.74 KOHmg / g and a hydroxyl value of 50.3 KO.
Hmg / g, freezing point was 62 ° C, and number average molecular weight was 2119.

Production Example 6 (Production of Isocyanate Prepolymer) In a four-necked flask, 100 parts of 4,4′-diphenylmethane diisocyanate was charged, the temperature was adjusted to 60 ° C., a stirring rod, a dehydrating tube, a nitrogen gas introducing tube, and A thermometer was attached.

Next, while vigorously stirring the contents in the flask, the polyester polyol A (72.5 parts) obtained in Preparation Example 1 was gradually dropped in a nitrogen stream at 40 ° C. Was kept at 50 to 70 ° C. and reacted for 2 hours.

Next, 11 parts of carbodiimide-modified MDI (manufactured by Nippon Polyurethane Co., Ltd., trade name: Coronate MX) was added to the flask, and the mixture was aged for 1 hour to obtain an isocyanate prepolymer (NCO%: 18.5%). , 6
(Viscosity at 0 ° C .: 225 cP).

Production Example 7 (Production of Isocyanate Prepolymer) In a four-necked flask, 100 parts of 4,4′-diphenylmethane diisocyanate was charged, the temperature was adjusted to 60 ° C., and a stirring rod, a dehydrating tube, a nitrogen gas introducing tube and A thermometer was attached.

Next, while vigorously stirring the contents in the flask, the polyester polyol B (72.5 parts) obtained in Preparation Example 2 was gradually dropped in a nitrogen stream at 40 ° C. Was kept at 50 to 70 ° C. and reacted for 2 hours.

Next, 11 parts of carbodiimide-modified MDI (manufactured by Nippon Polyurethane Co., Ltd., trade name: Coronate MX) was added to the flask, and the mixture was aged for 1 hour, followed by isocyanate prepolymer (NCO%: 18.5%). , 6
(Viscosity at 0 ° C .: 335 cP).

Production Example 8 (Production of Isocyanate Prepolymer) Since the polyester polyol C obtained in Preparation Example 3 has a high freezing point and cannot be dropped at 40 ° C., the polyester polyols C obtained in Preparation Examples 1 and 2 Polyol B
-C could not be handled.

Accordingly, it was not easy to produce a prepolymer using the polyester polyol obtained in Preparation Example 3.

Production Example 9 (Production of Isocyanate Prepolymer) An attempt was made to produce an isocyanate prepolymer in the same manner as in Production Examples 6 and 7 using the polyester polyol D obtained in Preparation Example 4.
Because of its high freezing point and viscosity, the temperature was controlled at 90 ° C as well as at 40 ° C, and an attempt was made to gradually drop it.
The charging pipe was clogged, and the desired isocyanate prepolymer could not be obtained.

Then, when the temperature of the polyester polyol D was further increased and the reaction was carried out in a state where it could be dropped, the reaction was runaway due to the heat generated by the prepolymerization reaction, resulting in gelation.

Examples 5 to 6 and Comparative Example 2 100 parts of polyester polyol A (starting monomers: ethylene glycol, diethylene glycol and adipic acid, number average molecular weight 2,200), 11 parts of ethylene glycol, 1.05 parts of water, triethylene diamine 0.8 part and 1 part of a silicone foam stabilizer were added and mixed to obtain a polyol component.

Next, the obtained polyol component and the isocyanate prepolymer or isocyanate prepolymer obtained in Production Examples 6 to 7 (trade name: manufactured by Kao Corporation)
B-2009, NCO%: 18.5%), and a polyurethane foam sheet was produced in the same manner as in Example 1.

The physical properties of the obtained polyurethane foam sheet were examined in the same manner as in Example 1. Table 2 shows the results.

Examples 7 to 8 and Comparative Example 3 60 parts of polyester polyol (raw material monomer: ethylene glycol, 1,4-butylene glycol, adipic acid, number average molecular weight 2,200) and polyester polyol (raw material monomer: ethylene glycol, 1,4-
40 parts of butylene glycol and adipic acid, number average molecular weight 1,300), 11 parts of ethylene glycol, 1.65 parts of water, 0.8 parts of triethylenediamine and 1 part of a silicone foam stabilizer are added and mixed to form a foam. Was obtained.

Next, the obtained polyol component and the isocyanate prepolymer or isocyanate prepolymer obtained in Production Examples 6 to 7 (trade name: manufactured by Kao Corporation)
B-2009, NCO%: 18.5%), and a polyurethane foam sheet was produced in the same manner as in Example 1.

The physical properties of the obtained polyurethane foam sheet were examined in the same manner as in Example 1. Table 2 shows the results.

[0126]

[Table 2]

From the results shown in Table 2, the polyurethane foam sheets obtained in Examples 5 to 9 were compared with Comparative Examples 2 to 3
It can be understood that the tensile strength and the tear strength are remarkably excellent while the density of the molded body is almost the same as in the case of

[0128]

According to the production method of the present invention, particularly in the molding of polyurethane foam such as polyurethane shoe soles, even if the density is low, the tensile strength, tear strength and the like are maintained without impairing the appearance and feeling. This has the effect that a polyurethane foam having significantly improved physical properties can be produced.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Akito Ihi, 1334 Minato, Wakayama City, Kao Corporation Research Laboratory (72) Inventor Makoto Okubo, 1334 Minato, Wakayama City, Kao Corporation Research Laboratory (56) References JP Akira 62-290723 (JP, A) JP-A-47-6990 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 63/00-63/91 C08G 18/00-18 / 87 CA (STN) REGISTRY (STN)

Claims (6)

(57) [Claims] 1. A consists of a (a) terephthalic acid and (b) adipic acid, and the acid component is 0.05 to 0.3 molar ratio of (a) terephthalic acid / (b) adipic acid, polyhydric Polyester polyol obtained by condensation polymerization of alcohol. 2. The polyester polyol according to claim 1, which has a number average molecular weight of 500 to 3,000. 3. The polyester polyol according to claim 1, wherein the polyhydric alcohol is ethylene glycol and / or 1,4-butanediol. 4. reacting a polyisocyanate component and a polyol component, a process for the preparation of polyurethane foams by foaming, the polyol component is composed of a (a) terephthalic acid and (b) adipic acid, (a) terephthalic (B) a polyurethane foam containing a polyester polyol obtained by condensation polymerization of an acid component having a molar ratio of adipic acid of 0.05 to 0.3 and a polyhydric alcohol; Production method. 5. The method for producing a polyurethane foam according to claim 4, wherein the content of the polyester polyol in the polyol component is 10 to 80% by weight. 6. A method for producing a polyurethane foam by reacting and foaming an isocyanate prepolymer prepared from a polyisocyanate component and a polyol component with a polyol component, wherein the polyol component used in the isocyanate prepolymer is (B) It consists a) terephthalic acid and (b) adipic acid, (a) an acid component molar ratio of terephthalic acid / (b) adipic acid is 0.05 to 0.3, by condensation polymerization of a polyhydric alcohol A method for producing a polyurethane foam, comprising a polyester polyol comprising: